This dissertation work is a study of the growth kinematics, synthesis strategies and intrinsic properties of InSb nanowires (NWs). The highlights of this work include a study of the effect of the growth parameters on the composition and crystallinity of NWs. A change in the temperature ramp-up rate as the substrate was heated to reach the NW growth temperature resulted in NWs that were either crystalline or amorphous. The as-grown NWs were found to have very different optical and electrical properties. The growth mechanism for crystalline NWs is the standard vapor-liquid-solid growth mechanism. This work proposes two possible growth mechanisms for amorphous NWs. The amorphous InSb NWs were found to be very sensitive to laser radiation and to heat treatment. Raman spectroscopy measurements on these NWs showed that intense laser light induced localized crystallization, most likely due to radiation induced annealing of defects in the region hit by the laser beam. Electron transport measurements revealed non-linear current-voltage characteristics that could not be explained by a Schottky diode behavior. Analysis of the experimental data showed that electrical conduction in this material is governed by space charge limited current (SCLC) in the high bias-field region and by Ohm's law in the low bias region. Temperature dependent conductivity measurements on these NWs revealed that conduction follows Mott variable range hopping mechanism at low temperatures and near neighbor hopping mechanism at high temperature. Low-temperature annealing of the amorphous NWs in an inert environment was found to induce a phase transformation of the NWs, causing their crystallinity to be enhanced. This thesis also proposes a new and low-cost strategy to grow p-type InSb NWs on InSb films grown on glass substrate. The high quality polycrystalline InSb film was used as the host on which the NWs were grown. The NWs with an average diameter of 150 nm and length of 20 μm were shown to have hole concentration of about 1017 cm-3 and mobility of about 1000 cm2V-1s-1. This thesis also proposes a strategy for the fabrication of metal-semiconductor nanocomposites. InSb NWs grown by electrochemical deposition were decorated with nanometer sized Au and Ag nanoparticles to form the nanocomposite.

Thesis (MSc)--Stellenbosch University, 2013. / ENGLISH ABSTRACT: The aim of this study was to develop a ZnO nanowire-array biosensor that would detect immunoglobulins and record changes in the concentration of an antibody. Early detection of disease-causing agents is essential for an early response. In contrast to conventional methods, biosensors may detect disease-associated agents much faster and more accurate, which holds specific benefits to rural communities. The development of such a biosensor would be favourable for diagnostics in underprivileged communities without infrastructure. The hypothesis was that binding of antibodies to the surface of ZnO nanowires would result in the generation of a piezoelectric potential that, when channelled through a Schottky barrier, would produce a constant voltage reading. Piezoelectricty would be generated due to the bending of the nanowires, or tensile stress applied to the nanowires due to binding of the antibodies. The performance of such a device largely depends on the methods used to construct the ZnO nanowires and methods used to funtionalize the sensor surface. The biggest challenge was thus to chemically modify the self-assembled monolayers (SAMs) and create intermediate monolayers that would react to primary amino groups of lysozyme and form a covalent amide bond. Lysozyme was selected as model antigen, since its structure and reaction with antibodies has been well studied. Alkanethiol and dialkyl disulphides were used to form SAMs. Different SAMs were compared to select the absorbate that would bind the highest concentration of lysozyme. Lysozyme was best immobilized onto Au film layers in the presence of SAM 3-mercaptopropionic acid. Weakest immobilization was in the presence of combined SAM 11-mercaptoundecanoic acid/1-nonanethiol. The sensitivity of the constructed ZnO nanowire biosensor was tested in vitro, in the presence of different concentrations of lysozyme antibodies. An increase in the dimension of the ZnO seed layer led to an increase in the mean diameter of the ZnO seed grains, and subsequently an increase in the mean diameter of the synthesized ZnO nanowires. Deposition of the ZnO seed layer, using the RF cylindrical magnetron sputtering technique, improved the c-axis alignment of the nanowires and produced nanowires with similar dimensions. However, deposition of the ZnO seed layer using the sol-gel spin coating technique, produced nanowires with irregular c-axis alignments and irregular diameters. An increase in the Au film thickness led to a decrease in the mean diameter of the synthesized ZnO nanowires and worsening of the c-axis alignment. In contrast to single crystalline Au (111) film layers, polycrystalline Au layers increased the mean diameter of the synthesized nanowires. The crystal orientation of the Au film layer had no effect on the c-axis alignment. Increased voltage readings were recorded with an increase in antibody binding, indicating that the ZnO nanosensor may be used to record changes in immunoglobulin levels. Antibody concentrations ranging from 10 ng/ml to 20 μg/ml were sensed. This is the first study showing that ZnO nanowires, conformed into piezoelectric transducers, may be used in the detection of antibodies. The current size of the chip with ZnO nanowires is approximately 1 cm², which is too big to incorporate into a compact monitoring device. Apart from the challenge to produce smaller nanowire-arrays, highly sensitive sensors and miniature amplifiers will have to be developed to increase the strength of the signals generated by the nanowires. The biosensor will also have to be optimised to detect a variety of immunoglobulins. / AFRIKAANSE OPSOMMING: Die doel van hierdie studie was om ‘n ZnO nanodraad biosensor te ontwikkel wat immunoglobuliene kan opspoor en veranderinge in konsentrasies van die teenliggaampies sal reflekteer. Vroë deteksie van siekte veroorsaakende agente is belangrik vir n vroeg tydige respons. In teenstelling tot konvensionele metodes, kan biosensors siekte veroorsaakende agente vining en akkuraat opspoor, wat veral voordele vir gemeenskappe in landelike gebiede inhou. Die hipotese was dat binding van teenliggaampies aan die ZnO nanodrade ‘n piëzo-elektriese potensiaal sal skep, wat dan ‘n konstante leesbare spanningspotensiaal sal lewer nadat dit deur ‘n Schottky versperring gestuur is. Piëzo-elektrisiteit word gegenereer deur die buiging van die nanodrade, of deur spanning wat op die nanodrade geplaas word deur binding van die teenliggaampies. Die sukses van die ontwerp hang grootliks af van die metode wat gebruik word om die ZnO nanodrade te konstrueer en metodes wat gebruik word om die sensor oppervlak te funksionaliseer. Die grootste uitdaging was dus om die monolae wat outomaties saam groepeer (SAMs) chemies so te verander dat intermediêre monolae vorm wat aan primêre aminogroepe van lisosiem bind ten einde kovalente amied-bindings te vorm. Lisosiem is as model antigeen geselekteer omdat die struktuur en reaksie daarvan met teenliggaampies reeds goed bestudeer is. Alkaantiol en di-alkiel disulfied is gebruik om SAMs te vorm. ‘n Verskeidenheid SAMs is vergelyk ten einde die anker te selekteer waaraan die hoogste konsentrasie lisosiem sal bind. Lisosiem is die effektiefste aan Au film lae ge-immobiliseer in die teenwoordigheid van SAM 3-merkapto-propanoësuur. Die swakste immobilisasie is in die teenwoordigheid van kombineerde SAM 11-merkapto-dekanoësuur/1-nanotiol waargeneem. Die sensitiwiteit van die ZnO nanodrade is in vitro getoets, in die teenwoordigheid van verskillende konsentrasies van lisosiem teenliggaampies. ‘n Toename in die dimensie van die ZnO grondlaag het die gemiddelde deursnit van die ZnO grein verhoog en so ook die gemiddelde deursnit van die gesintetiseerde ZnO nanodrade. Toediening van die ZnO grondlaag deur gebruik te maak van die RF silindriese mikrogolf-verstuiwings tegniek het die orientasie van die c-aslyn van die nanodrade verbeter. Toediening met die sol-gel draai-bedekkings tegniek het ‘n onreëlmatige orientasie van die c-aslyn teweeg gebring, asook ‘n variasie in die afmetings van die nanodrade. ‘n Toename in die Au laag het ‘n afname in die gemiddelde afmetings van die nanodrade en ook ‘n onreelmatige oriëntasie van die c-aslyn veroorsaak. In teenstelling met enkel-kristallyne Au (111) het poli-kristallyne Au lagies ‘n toename in die gemiddelde deursnit van die nanodrade veroorsaak. Die kristal-oriëntasie van die Au laag het geen effek op die belyning van die nanodrade gehad nie. Die spanningspotensiaal het verhoog met ‘n toename in teenliggaampie binding. Hiervolgens kan die ZnO nanosensor gebruik word om veranderinge in immunoglobulien vlakke te monitor. Teenliggaampie konsentrasies wat wissel van 10 ng/ml tot 20 μg/ml is opgespoor. Hierdie is die eerste studie wat toon dat ZnO nanodrade, omskep tot piëzo-elektriese transduseerders, gebruik kan word in die opsporing van teenliggaampies. Die grootte van die skyfie met die ZnO nanodrade is tans ongeveer 1 cm² en is te groot om in ‘n kompakte biosensor in te bou. Benewens die uitdaging om kleiner nanodraad skyfies te ontwikkel, sal hoogs sensitiewe sensors en seinversterkers ontwikkel moet word om die sein afkomstig van die nanodrade te versterk. Die biosensor sal ook ge-optimiseer moet word om ‘n verskeidenheid immunoglobuliene op te spoor.

Interest in nanomaterials is motivated partly by their potential for sensor arrays to detect different gases. Nanowires in particular are of interest because their high surface-to-volume ratio promises the possibility of high sensitivity. However, because of their discrete quasi-one-dimensional geometry, electrical integration of nanowires into photolithographically defined devices and circuits is challenging and remains one of the obstacles to their widespread use. In this thesis, a novel method for fabricating electrically integrated zinc oxide nanobridge devices using carbonized photoresist is investigated. The conductivity of carbonized photoresist is known and nanowire growth on carbonized photoresist has recently been reported, suggesting the possibility of simultaneous use as a nucleation layer and electrode. However, these reports did not characterize the contact between the ZnO nanowires and carbonized photoresist. In this work, ZnO nanobridges are fabricated between opposing carbonized photoresist electrodes and characterized both electrically and with electron microscopy. Operation of nanobridge devices as bottom gate transistors, UV sensors, and gas sensors is demonstrated. / Graduation date: 2010

Recent advances in third generation photovoltaics, particularly the rapid increase in perovskite power conversion efficiencies, may provide a cheap alternative to silicon solar cells in the near future. A key component to these devices is the transparent front electrode, and in the case of Dye Sensitized Solar Cells, it is the most expensive part. A lightweight, cost-effective, robust, and easy-to-fabricate new generation TCE is required to enable competition with silicon. Indium Tin Oxide, commonly used in touchscreen devices, Organic Light Emitting Diodes (OLEDs), and thin film photovoltaics, is widely used and commonly referred to as the industry standard. As the global supply of indium decreases and the demand for this TCE increases, a similar alternative TCE is required to accompany the next generation solar cells that promise energy with lighter and significantly cheaper modules. This alternative TCE needs to provide similar sheet resistance and optical transmittance to ITO, while also being mechanically and chemically robust. The work in this thesis begins with an exploration of several synthesized ITO replacement materials, such as copper nanowires, conductive polymer PEDOT:PSS, zinc oxide thin films, reduced graphene oxide and combinations of the above. A guiding philosophy to this work was prioritizing cheap, easy deposition methods and overall scalability. Shortcomings of these TCEs were investigated and different materials were hybridized to take advantage of each layers strengths for development of an ideal ITO replacement. For CuNW-based composite electrodes, ~85% optical transmittance and ~25 Ω/sq were observed and characterized to understand the underlying mechanisms for optimization. The second half of this work is an examination of many different perovskite synthesis methods first to achieve highest performance, and then to integrate compatible methods with our CuNW TCEs. Several literature methods investigated were irreproducible, and those that were successful posed difficulties integrating with CuNW-based TCEs. Those shortcomings are discussed, and how future work might skirt the issues revealed here to produce a very low cost, high performance perovskite solar cell.

Discover of new energy sources and solutions are one of the important global issues nowadays, which has a big impact on economy as well as environment. One of the methods to help to mitigate this issue is to recover wasted heat, which is produced in large quantities by the industry, through vehicle exhausts and in many other situations where we consume energy. One way to do this would be using thermoelectric (TE) materials, which enable direct interconversion between heat and electrical energy. This thesis investigates how the novel material combinations and nanotechnology could be used for fabricating more efficient TE materials and devices. The work presents synthesis, processing, and electrical characterization of group IV materials for TE applications. The starting point is epitaxial growth of alloys of group IV elements, silicon (Si), germanium (Ge) and tin (Sn), with a focus on SiGe and GeSn(Si) alloys. The material development is performed using chemical vapor deposition (CVD) technique. Strained and strain-relaxed Ge1-x Snx (0.01≤x≤0.15) has been successfully grown on Ge buffer and Si substrate, respectively. It is demonstrated that a precise control of temperature, growth rate, Sn flow and buffer layer quality is necessary to overcome Sn segregation and achieve a high quality GeSn layer. The incorporation of Si and n- and p-type dopant atoms is also investigated and it was found that the strain can be compensated in the presence of Si and dopant atoms.  Si1-xGexlayers are grown on Si-on-insulator wafers and condensed by oxidation at 1050 ᵒC to manufacture SiGe-on-insulator (SGOI) wafers. Nanowires (NWs) are processed, either by sidewall transfer lithography (STL), or by using conventional lithography, and subsequently manufactured into nanoscale dimensions by focused ion beam (FIB) technique. The NWs are formed in an array, where one side is heated by a resistive heater made of Ti/Pt. The power factor of NWs is measured and the results are compared for NWs manufactured by different methods. It is found that the electrical properties of NWs fabricated with FIB technique can be influenced due to Ga doping during ion milling. Finally, the carrier transport in SiGe NWs formed on SGOI samples is tailored by applying a back-gate voltage on the Si substrate. In this way, the power factor is improved by a factor of 4. This improvement is related to the presence of defects and/or small fluctuation of nanowire shape and Ge content along the NWs, generated during processing and condensation of SiGe layers. The SiGe results open a new window for operation of SiGe NWs-based TE devices in the new temperature range of 250 to 450 K. / <p>QC 20160907</p>

Chemical sensors based on arrays of polymer-coated surface acoustic wave (SAW) devices are required for defense applications that provide a combination of sensitivity, selectivity, portability and response time. The primary challenge in the development of these polymer-based microsensors is the need to reproducibly deposit high quality, defect-free polymer coatings onto microelectrodes. Coating methods such as air brushing and solvent casting have proven unreliable and I have investigated the possibility of depositing polymer films on microelectrodes using electrostatic processing methods. In this work AC electrospraying was used to deposit nanoscale polymer films onto the surface of microelectrodes. The alternating polarity of the electric field eliminates surface charge accumulation and the polymers were deposited uniformly across both electrically insulating and conducting surface regions. In a different work, DC electrospraying was used to deposit patterned organic coatings onto the surface of microelectrodes. The surface of the microelectrode array consisted of an alternating pattern of insulating, grounded-metallic and ungrounded metallic regions, each with a width of 15µm. The charged particles were deposited only onto the grounded-metallic surface regions where there is an electrical path for charge dissipation. No polymer deposition was observed on the insulating or ungrounded-metallic regions due to the effects of surface charge accumulation. Also, I, DC electrodeposited organic molecules within the pores of ceramic film. Due to electrospraying, this film has a strong built-in electric field that induces Stark effect in the organic molecules, providing a unique new technology for bio and chemical sensing. Electrospinning has been used to produce polymer nanofibers with diameters ranging from a few microns to less than 100 nanometers. Due to mechanical oscillations of the electrically charged fibers during electrospinning, they are usually collected in the form of a non-woven mat without any significant fiber orientation. I have developed a new method for making highly aligned arrays of polymer nanofibers by using an AC coupled DC field to drive the electrospinning process. This new "biased AC electrospinning" method can be used to deposit aligned arrays of polymer nanofibers onto virtually any substrate. Potential applications of well-ordered nanofiber materials include tissue engineering, filtration, drug delivery and microelectronics.

Mimicking the biological olfactory systems that consist of olfactory receptor arrays with large surface area and massively-diversified chemical reactivity, three dimensional (3D) metal oxide nanowire arrays were used as the active materials for gas detection. Metal oxide nanowire arrays share similar 3D structures as the array of mammal's olfactory receptors and the chemical reactivity of nanowire array can be modified by surface coatings. In this dissertation, two standalone gas sensors based on metal oxide nanowire arrays prepared by microfabrication and in-situ micromanipulation, respectively, have been demonstrated. The sensors based on WO3 nanowire arrays can detect 50 ppb NO2 with a fast response; well-aligned CuO nanowire array present a new detection mechanism, which can identify H2S at a concentration of 500 ppb. To expand the material library of 3D metal oxide nanowire arrays for gas sensing, a general route to polycrystalline metal oxide nanowire array has been introduced by using ZnO nanowire arrays as structural templates. The effectiveness of this method for high performance gas sensing was first investigated by single-nanowire devices. The polycrystalline metal oxide coatings showed high performance for gas detection and their sensitivity can be further enhanced by catalytic noble metal decorations. To form electronic nose systems, different metal oxide coatings and catalytic decorations were employed to diversify the chemical reactivity of the sensors. The systems can detect low concentrated H2S and NO2 at room temperature down to part-per-billion level. The system with different catalytic metal coatings is also capable of discriminiating five different gases (H2S, NO2, NH3, H2 and CO).

Systems of magnetic nanowires are considered strong candidates in many technological applications as microwave filters, sensors or devices for data storage. Because of their strong potential as candidates in such applications they became lately the object of many studies. However, due to the very complicated nature of the interwire interactions, their magnetic behavior is very difficult to be interpreted. The main parameter controlling the response of magnetic nanowires assemblies is the aspect ratio of the nanowires that is defined as the ratio of the length to the wire's diameter. In our study we choose to modify the aspect ratio by keeping a constant length of nanowires and modifying the wire's diameter while keeping the same interwire distance. The samples were studied at room temperature, using vibrating sample magnetometer and X-band ferromagnetic resonance experiments. The results are explained taking into account the effects of the magnetostatic interactions and shape anisotropy.

The work in this thesis is divided in three parts. In part one we developed electrodeposition method of Nickel Nanowire in commercial AAO template in constant current (Galvanostatic) mode, further we tried to estimate the growth rate from theory, from saturation magnetization and direct measurement from SEM image. In part two we focused on using the Vector Network Analyzer (VNA) to measure the Ferromagnetic Resonance (FMR))of various magnetic Nanowire arrays. We employed different measurement geometries using microstripline and coplanar waveguide as microwave transmission lines. In part three our aim was to study the magnetic properties of complex ferromagnetic system, especially the effect of interactions on dynamic properties of magnetic nanostructures (nanowire arrays and exchange biased ferromagnetic-antiferromagnetic multilayers). Our effort was centered on using ferromagnetic resonance to understand the dynamic response of these systems.

To build novel electronic noses for mimicking biological olfactory systems that consist of olfactory receptor arrays with large surface area and massively-diversified chemical reactivity, three dimensional (3D) vertical aligned ZnO nanowire arrays were employed as active materials for gas detection. ZnO nanowire arrays share 3D structures similar to mammalian olfactory receptor arrays, with thousands of vertical nanowires providing a high reception area which can significantly enhance the sensors’ sensitivity. Meanwhile, with different material decorations (such as SnO2, In2O3, WO3 and polymers), each array of nanowires can produce a distinguishable response for each separate analyte, which would provide a promising way to improve the selectivity. Both patterned grown well-aligned and wafer size random-distributed 3D nanowire array sensing devices are investigated. Several different types of gas sensors have been investigated in this dissertation. Metal oxide semiconductor gas sensors based on 3D metal oxides/ZnO vertical nanowire arrays have detected NO2 and H2S down to ppb level, and five gases of NO2, H2S, H2, NH3, and CO have been discriminated. Active self-powered gas sensors based on 3D metal oxides/ZnO vertical nanowire arrays have been successfully fabricated and worked well for H2S and NO2 detection. With the decoration by mixture of PEDOT polymer with metal oxide nanoparticles, ZnO vertical nanowire array gas sensors have fast response and recovery time as well as good sensitivity to volatile organic gases of acetone, methanol and ethanol. A novel ionization sensor also has been built by ZnO vertical nannowire arrays, and this device could be able to ionize air under safety operation voltage.